Ha Noi 2019
MINISTRY OF EDUCATION AND
TRAINING
VIETNAM ACADEMY OF
SCIENCE
AND TECHNOLOGY
GRADUATE UNIVERSITY SCIENCE AND TECHNOLOGY
……..….***…………
PHAM VAN THINH
SYNTHESIS OF MAGNETIC MATERIALS ON GRAPHITE
VIETNAM APPLICATION IN ENVIRONMENTAL TREATMENT
OF ORGANIC POLLUTION (CONGO RED)
Major: Polymeric And Composite Materials
Code: 9440125
SUMMARY OF POLYMERIC AND COMPOSITE MATERIALS
DOCTORAL THESIS
Science instructor 1: Associate Professor Ph.D. Bach Long Giang
Science instructor 2: Associate Professor Ph.D. Le Thi Hong Nhan
Reviewer 1:
Reviewer 2:
Reviewer 3: ….
The dissertation will be defended in front of the Ph.D. Thesis, meeting at the
Academy Of Science And Technology - Graduate University Science And
Technology - Vietnam at hours.., day … month year 201….
The dissertation can be found at:
- Library of Graduate University Science And Technology
- Vietnam National Library
The work was completed at Graduate University Science And
Technology - Vietnam Academy of Science And Technology
1
PREAMBLE
1. The urgency of the thesis
The current, Environmental pollution issues such as textile color
pollution, Dyeing are becoming an urgent issue in Vietnam as well as in the
world. It directly affects the lives, health, and activities of the people.
The methods of handling color pollution are very diverse. However,
they still exist certain limitations such as low efficiency, Complex operation,
creating environmental unfriendly byproducts that limit their potential.
Based on the very good properties of magnetic materials, the thesis aims
to use this hybrid material for the environmental treatment process of toxic
organic pigments. Focus on synthesizing magnetic materials (EG @
MFe2O4) of Ni, Co, and Mn metals to enhance adsorption capacity with
exfoliated graphite. EG @ MFe2O4 material is used to adsorb dye pollution
(CR). In particular, the research results focus on evaluating and analyzing
optimal adsorption parameters, kinetics, thermodynamics, adsorption
isotherms, adsorption mechanism, and material recycling ability.
2. Research objectives of the thesis
Researching and developing technology for producing magnetic
graphite materials from Vietnamese flake graphite sources as materials to
be applied in treating the organic polluted environment.
3. The main research content of the thesis
- Researching and synthesizing exfoliating graphite (EG) material from
graphite source in Yen Bai province, Viet Nam by the chemical method
under microwave support.
- Research on the synthesized process of magnetic bearing EG-MFe2O4 (M
= Co, Ni, Mn) from graphite materials by the sol-gel method.
- Analyze and identify some typical properties, structure, morphology and
magnetism of EG and EG-MFe2O4 materials by modern analytical tool
methods such as: X-ray diffraction spectroscopy (XRD), X-ray energy
scattering spectroscopy (EDS), scanning electron microscopy (SEM),
2
infrared spectral analysis (FTIR), vibration magnetometer (VSM) analysis,
lines Adsorption / desorption curve N2 (BET, pore), XPS.
- Research and evaluate Congo red color adsorption capacity of EG-
MFe2O4 materials; kinetic studies, thermodynamics, adsorption isotherms,
adsorption mechanisms and application of RSM surface response methods
to optimize color adsorption conditions of materials.
CHAPTER 1. OVERVIEW
1. Graphite source material
Graphite, also known as graphite, is one of the three polymorphs of
carbon that exists in nature (diamonds, amorphous coal, and graphite).
Graphite is a crystalline substance in the hexagonal system. In the crystal
lattice, a carbon atom (C) linked to 4 C atoms is adjacent to the distance with
3 different C atoms (about 1.42 Å), and the distance to the 4th atom is 3,35
Å. Currently, the worldwide graphite ore reserves are not specifically listed,
however, it is estimated at 390 thousand tons. In Vietnam, according to
geological exploration reports, graphite is found in Lao Cai, Yen Bai and
Quang Ngai with total resources and reserves of 29,000 tons.
1.2.4. Overview of material manufacturing methods exfoliated graphite
(EG)
The creation of EG materials is usually done by rapid heating of the
interleaved compound, which can be carried out by various heating systems
including induction plasma, laser irradiation, and flame heating. In 1983,
Inagaki and Muranmatsu introduced an EG-making method that does not
use acids, but uses and decomposes tertiary compounds potassium-graphite-
tetrahydrofuran and has investigated several applications based on this new
material. In 1985, author S.A. Alfer et al. Investigated the high temperature
physical and chemical properties of anodized graphite oxidation products in
solid H2SO4 as a raw material to produce a new form of graphite - thermally
excreted graphite (TEG) and fabricated products. The word TEG has been
3
widely used.
In 1991, Y. Kuga and colleagues studied a method of crushing graphite
compounds alternating with potassium K-GIC and exfoliating graphite K-
EG in a vacuum. In 1991, Yoshida and colleagues also successfully
researched in the production of various insertion compounds such as
insertion with H2SO4, FeCl3, Na-tetrahydrofuran (THF), K-THF and Co-
THF. The interleaved compounds were then rapidly heated to 1000 0C to
expand the graphite.
In summary, through the analysis of the research results of the authors
who came before the thesis, we will choose the method of synthesizing EG
materials by chemical methods with the insertion agent of H2SO4 and H2O2
under the support of microwaves. Civil, in order to combine the good criteria
such as simple method, low cost, and high adsorption efficiency. At the
same time under the microwave support to shorten the synthesis time as well
as improve the efflux efficiency of graphite.
1.3. Magnetic materials
1.3.1. Synthesis of EG@MFe2O4 materials
Cobalt ferrite, nickel ferrite, and manganese ferrite are very important
spinel ferrite in engineering. Structurally, cobalt ferrite and nickel ferrite
crystals are typical of spinel ferrite group, face centered cubic structure.
They are the reverse spine, Because the electron configuration of Ni2+ ions
is 3d8, of Co2+ ion, is 3d7, the favorable coordination number is 6, so Ni2+
and Co2+ ions are in octahedral holes and Fe3+ ions are distributed in both
octahedral and tetrahedral holes.
There are two approaches to synthesizing spine ferritic material: the
approach from the top and the bottom. The top-down approach uses physical
methods, while the bottom-up approach is usually done by chemical
pathways. Methods of synthesis by chemical colloid can control the particle
size, the collected nanoparticles have uniform size, rich shape. Typical
chemical methods commonly used include precipitation, reduction,
explosion, thermal decomposition hot spray, micelles (reverse), sol-gel
process, flocculation directly in high boiling solvents, hydro heat. The